This thesis aims to utilize graphene nanoplatelets (GNPs) in biobased and biodegradable thermoplastic polylactide (PLA) matrix for improved properties and multifunctionalities. A comprehensive comparative study was carried out on the effect of the addition of GNPs with different sizes. The mechanical, electrical, thermal and barrier properties of resulting PLA/GNP nanocomposites and their inter-relationship with the microstructure of the composites is revealed. The effect of annealing on dynamic percolation and conductive network formation of PLA/GNP composites including the effect of hybrid GNP fillers of different size is reported, indicating the underlying mechanisms for different behaviours of GNP fillers of different size. Multifunctional engineering biopolymers with improved performances (mechanical and electrical) and added functionalities (barrier properties) were successfully developed through controlled filler distribution and orientation using multilayer co-extrusion technology. Changes in mechanical properties of the PLA/GNP multilayer nanocomposites were successfully correlated with GNP orientation in the filled layers. Multilayer PLA/GNP nanocomposites demonstrated excellent mechanical and barrier properties with low filler loadings compared to traditional mono-extruded films.

Graphene Nanoplatelets (GNP) was incorporated into polyamide 6 (PA6) matrix by melt compounding method and the enhancements in the properties of the nanocomposites were studied. Response Surface Methodology (RSM) was employed to assist in the study of processing conditions in melt compounding. RSM analysis revealed that the GNP concentrations to be the most significant term to affect the tensile modulus and crystallinity followed by the screw speed whereas the residence time was found to be non-significant. GNP with 5 Î1⁄4m (G5) and 25 Î1⁄4m (G25) were used in the GNP aspect ratio study. The average flake size of G5 and G25 to was measured to be 5.07 Î1⁄4m and 22.0 Î1⁄4m, respectively with the G5 distributed narrowly whereas the G25 exhibit broad distribution. TGA analysis shown that HT25 is more thermally stable compared to G25 due to some remnants lost during thermal treatment and this was confirmed by EDX and CHNS analysis. XRD profiles of the PA6-G-NC illustrate typical peaks of PA6 crystals phase as well as pure graphite characteristic peak. PA6-G25-NC observed to exhibit slightly higher peak intensity compared to PA6-G5-NC suggesting more formation of PA6 crystals. Similar improvement was observed on PA6-HT25-NC compared to PA6-G25-NC indicating more formation of PA6 crystals due improved dispersion of HT25. DSC on PA6-G25-NC showed higher cooling temperature and crystallinity compared to PA6-G5-NC due to larger surface area of the G25. Similarly, PA6-HT25 showed better improvement in crystallinity over PA6-G25-NC due to increase nucleation sites by the HT25. The thermal conductivity of PA6-G25-NC is slightly higher than the thermal conductivity of PA6-G5-NC but not significant considering the G25 is 5 times larger than G5. Instead, no significant difference was observed between PA6-HT25-NC and PA6-G25-NC. Addition of GNP increased the thermal stability of the PA6-G-NC systems under both nitrogen and air atmospheres regardless of the GNP aspect ratio. The viscoelastic properties showed insignificant difference between PA6-G5-NC and PA6-G25-NC. The inefficient improvement by G25 might be due to agglomeration formed during processing. The storage modulus and tan Î ́ of PA6-HT25-NC decreased but the Tg significantly improved compared to PA6-G25-NC. This was assumed to be because of improved dispersion of HT25 but reduced interfacial interaction after the heat treatment. The shear storage modulus, G’ and complex viscosity, |η*| were observed to increase with increasing GNP content with more pronounced improvement seen on PA6-G25-NC compared to PA6-G5-NC. However, no network percolation threshold was observed until 20 wt.% of GNP. The poor interfacial interaction of HT25 resulted in lower G’ and |η*| compared to G25. Tensile test results showed typical improvement with PA6-G25-NC having higher tensile modulus compared to PA6-G5-NC. Further enhancement was obtained with PA6-HT25-NC suggesting improved dispersion and volume of constrained chains mobility despite the poor surface interaction. Comparison with Halphin-Tsai modulus revealed that the effective modulus to be 150 GPa for G5 and 200 GPa for G25. The water uptake measurement results showed that GNP reduced the water uptake percentage and diffusion coefficient especially with G25. The test conducted on saturated PA6-G-NC results in improved thermal conductivity due to the high thermal conductivity of water but the viscoelastic and tensile properties severely reduced due to plasticisation effect.

In the last decade, carbon nanotubes (CNTs) and Graphene nanoplatelets (GNPs) have attracted a lot of attentions in various polymeric and ceramic composite systems, in an effort to improve their mechanical and functional properties. Al2O3 has attracted considerable interests in ceramics community, in particular as a matrix material for composite fabrications. The high stiffness, excellent thermal stability and chemical resistance of Al2O3 make it practically a very important engineering material, and if we can overcome its brittleness issue, its applications will be much wider. Adding CNTs as a reinforcement to the Al2O3 matrix to improve the toughness is one of the most promising methods. Similarly, GNPs have recently also been shown to be very promising for the same purpose. It has been demonstrated that by adding a mixture of the 2D-GNPs and 1D-CNTs into a polymer matrix, the toughest or strongest man-made ropes have been made. However, the homogenous dispersion of CNTs or GNPs is more of a challenge in a ceramic matrix than in polymeric matrices, owing to the tendency of CNT agglomerations and more steps are needed to completely transfer the useful properties of CNTs and GNPs into ceramics. In this thesis, nanocomposites of Al2O3 reinforced with a hybrid of GNTs (a blend of GNPs and CNTs) were first fabricated. The hybrid GNT reinforcements were mixed with the Al2O3 using a wet chemical technique under ultrasonic treatment. The effects of varied GNT contents on the microstructural features and mechanical properties of the nanocomposites were then investigated. It is found that the well-dispersed GNT fillers resulted in high sintered densities (>99%) in the composites, whilst the fracture mode alteration, grain refinement and improved flexural strength of the composites are all associated with the inclusion of CNTs and GNPs. The average fracture toughness of the nanocomposites reached up to 5.7 MPa·m1/2, against 3.5 MPa·m1/2 of the plain Al2O3, and the flexural strength improved from 360 MPa to 424 MPa respectively, at a hybrid addition of 0.5 wt% GNPs and 1 wt% CNTs. The toughening mechanisms attributed with the unique morphologies and structures of the GNT fillers were also discussed based on analyses on the morphology, grain sizes and fracture mode. The effects of hot-pressing (HP) and spark plasma sintering (SPS) methods on the grain size, microstructural features, and mechanical behaviour of GNT-reinforced Al2O3 nanocomposites were then comprehensively studied. Identical overall reinforcement contents at various GNP/CNT ratios were selected to prepare the composites using both HP and SPS. Highly densified samples (>98%) were obtained at 1650°C under 40 MPa in Ar atmosphere, with dwell times of 1 h and 10 min for HP and SPS respectively. Both types of sample showed a mixture of inter- and trans-granular fracture behaviour. A 50% grain size reduction was observed for samples prepared by HP, compared with the SPS samples. Both types of samples achieved a high flexural strength and fracture toughness of > 400 MPa and 5.5 MPa·m1/2, respectively, whilst the properties of the SPS samples peaked at relatively lower GNT contents than those of the HP samples. Based on analyses of the morphology, grain sizes and fracture mode, similar toughening mechanisms for both types of sample were observed, involving the complex characteristics of the combined GNT fillers. The tribological performance of the HPed pure Al2O3 and its composites containing various hybrid GNT contents was further evaluated under different loading conditions using a ball-on-disc method. Benchmarked against the pure Al2O3, the composite reinforced with a 0.5 wt% GNP exhibited a 23% reduction in the friction coefficient along with a promising 70% wear rate reduction, and a hybrid reinforcement consisting of 0.3 wt.% GNPs + 1 wt.% CNTs resulted in even better performance, with a 86% reduction in the wear rate. The extent of damage to the reinforcement phases caused during wear was studied using Raman spectroscopy. The wear mechanisms for the composites were analysed according to the mechanical properties, brittleness index and microstructural characterization. The combination between GNPs and CNTs contributed to the excellent wear resistance properties for the hybrid GNT-reinforced composites. The GNPs played an important role in the formation of a tribofilm on the worn surface by exfoliation; whereas the CNTs contributed to the improvement in fracture toughness and prevented the grains being pulled out during the tribology test. Finally, Graphene Oxide (GO) was used to replace the GNPs in the hybrid, to prepare Al2O3-GONT nanocomposites, by adopting a new sol-gel processing, in addition to powder mixing. It has been found that sol-gel process leads to an impressive grain size reduction of 62%, the fracture toughness and flexural reached 6.2 MPa·m1/2 and 420 MPa (i.e. 70% and 14% improvement), respectively, than those of pure Al2O3, which even marginally outperformed the previously optimised Al2O3-GNP nanocomposites by 8% in fracture toughness. The success of our new sol-gel strategy opens up new opportunities for choosing hybrid reinforcements for the fabrication of advanced ceramic nanocomposites.

This thesis reports the effects of incorporating graphite nanoplatelets (GNPs) to epoxy-carbon fibre (CF) laminates to produce multiscale composites. A grade of epoxy resin typical for the application in aerospace engineering, triglycidyl-p-aminophenol (TGPAP), was used in this work cured with 4,4'-diaminodiphenyl sulfone (DDS). To improve the processability of TGPAP, a diluent, the diglycidyl ether of bisphenol F (DGEBF), was added to formulations. Compositions of TGPAP/DGEBF/DDS were optimised using response surface methodology (RSM) with the target response being to obtain high glass transition temperature (Tg) and low resin viscosity. From RSM, the optimum values were obtained at 55.6 wt. % of DGEBF and a stoichiometric ratio of 0.60. Before addition into epoxy, GNPs were treated either covalently using 3-aminopropyltriethoxysilane (APTS) or non-covalently using a commercial surfactant, Triton X-100 (abbreviated as A-GNPs and T-GNPs, respectively). After treatment, XPS analysis showed a new peak at 100 eV for A-GNPs indicating silicon and the C/O ratio increased from 11.0 to 26.2 for T-GNPs relative to unmodified GNPs (U-GNPs), suggesting attachment of the modifier molecules had occurred. Nanocomposites (NCs) were prepared by incorporate GNPs into epoxy using mechanical mixing. Rheological percolation threshold of GNP-epoxy suspensions were determined using oscillatory-shear rheometry as 3.9 wt. % for AR-GNPs, 3.6 wt. % for U-GNPs, 3.2 wt. % for A-GNPs and 3.5 wt. % for T-GNPs, suggesting surface treatment improved dispersion. At 4 wt. % of GNPs, flexural strain of NCs was decreased relative to neat epoxy by 46% for AR-GNPs, 48.6% for U-GNPs, 4.6% for A-GNPs and 30.8% for T-GNPs but flexural moduli showed small increases of 6.1-7.4%. Fracture toughness (K1C) also improved. For example, the K1C increased from 0.80 ± 0.04 MPa.m1/2 for neat epoxy to 1.32 ± 0.01 MPa.m1/2 for NCs containing 6 wt. % of U-GNPs possibly due to the branching of cracks resulting from the embedded GNPs. Due to their mechanical performance, A-GNPs were used to fabricate epoxy/CF/A-GNPs multiscale composites. Multiscale composites showed inferior properties relative to a comparable conventional composite in flexural testing, interlaminar shear strength (ILSS) and interlaminar fracture toughness mode II (G11C) due to weaker bonding at the matrix-CF interface. However, multiscale composites showed ~40% higher capability than conventional composite to absorb energy during impact due to greater interfaces formed by the inclusion of A-GNPs into the system.

The effects of high loading rates (HLR), and nano reinforcement on the mechanical response of adhesively-bonded SLJs with composite adherends, subjected to different loading (strain) rates are systematically investigated. The results are then compared to those of neat thermoset resin and thermo-plastic adhesive. More specifically, nano-reinforced and neat resin bonded joints mating carbon/epoxy and glass/epoxy adherends were subjected to tensile loadings under 1.5 and 3 mm/min and tensile impacts at a loading rate of 2.04E+5 mm/min. In some cases, additional tests were conducted under 15, 150, and 1500 mm/min to obtain additional properties gained using the nano-reinforcements for use in the further numerical investigations. The HLR tests were conducted, using a modified instrumented pendulum equipped with a specially designed impact load transfer apparatus. The dispersion of nanoparticles was facilitated using a mechanical stirrer and a three-roll mill machine. The failure mechanisms were studied with a scanning electron microscope.

Over the past years, research efforts have focused on adding highly conductive nanoparticles, such as carbon nanotubes (CNTs) and graphene nanoplatelets (GNPs), into polymers to improve their electrical conductivity or to tailor their piezoresistive behavior. Resultant materials are typically described by the weight or volume fractions of their nanoparticles. The weight/volume fraction alone is a very global quantity, making it a poor evaluator of a doping configuration. Knowing which particles actually participate in improving electrical conductivity can optimize the doping strategy. Additionally, conductive particles are only capable of charge transfer over a very short range, thus most of them do not form part of the conduction path. Thus, understanding how these particles are arranged is necessary to increase their efficiency. First, this work focuses on polymers loaded with CNTs. A computational modeling strategy based on a full morphological analysis of the CNT network is presented to systematically analyze conductive networks and show how particles are arranged. A definition of loading efficiency is provided based on the results obtained from this morphology analysis. This study provides useful guidelines for designing these types of materials based on important features, such as representative volume element, nanotube tortuosity and length, tunneling cutoff distance, and efficiency. Second, a computational approach is followed to study the conductive network formed by hybrid particles in polymer nanocomposites. These hybrid particles are synthesized by growing CNTs on the surfaces of GNPs. The objective of this study is to show that the higher electrical conductivity of these composites is due to the hybrids forming a segregated structure. Polymers loaded with hybrid particles have shown a higher electrical conductivity compared with classical carbon fillers: only CNTs, only GNPs or mixed CNTs and GNPs. This is done to understand and compare the doping efficiency of the different types of nanoparticles. Finally, some parameters of the hybrid particle are studied: CNT density on GNPs, and CNT and GNP geometries. Recommendations to further improve the composite’s conductivity based on these parameters are presented. It is noted that this work is the first time the hybrid particle is studied through a computational approach.

No description available.

The discovery of carbon nanotubes in 1990s popularized a new area of research in materials science called Nanoscience. In the following decades, several carbon based nanoparticles were discovered or engineered and with the discovery of Graphene nanoplatelets (GNP) in 2010, carbon based nanoparticles were propelled as the most promising class of nanoparticles. High mechanical strength and stiffness, excellent electrical and thermal conductivity, and high strength to weight ratios are some of the unique abilities of CNTs and GNPs which allow their use in a wide array of applications from aerospace materials to electronic devices. In the current work presented herein, CNTs and GNPs are added to polymeric materials to create a nanocomposite material. The effects of this nanoparticle addition (a.k.a reinforcement) on the mechanical properties of the nanocomposite polymer materials are studied. Specifically, efforts are focused on studying fracture toughness, a material property that describes the material's ability to resist crack growth. Relative to the conventional metals used in structures, epoxy-based composites have poor fracture toughness. This has long been a weak link when using epoxy composites for structural applications and therefore several efforts are being made to improve their fracture toughness. In the first, second and third chapters, the enhancement of fracture toughness brought about by the addition of carbon nanotubes (CNTs) and graphene nanoplatelets (GNPs) was investigated. CNT-Epoxy and GNP-Epoxy Compact Tension (CT) samples were fabricated with 0.1% and 0.5% nanofiller weight concentrations. The potential synergistic effects of dual nanofiller reinforcements were also explored using CNT/GNP-Epoxy CT samples at a 1:3, 3:1 and 1:1 ratio of CNT:GNP. Displacement controlled CT tests were conducted according to ASTM D5045 test procedure and the critical stress intensity factor, $K_{IC}$, and the critical fracture energy, $G_{IC}$, were calculated for all the material systems. Significant enhancements relative to neat epoxy were observed in reinforced epoxies. Fracture surfaces were analyzed via scanning electron microscopy. Instances of CNT pullouts on the fracture surface were observed, indicating the occurrence of crack bridging. Furthermore, increased surface roughness, an indicator of crack deflection, was observed along with some crack bifurcations in the GNP-Epoxy samples. In the fourth chapter of Part I, the influence of pre-crack characteristics on the Mode-I fracture toughness of epoxy is investigated. Pre-crack characteristics such as pre-crack length, crack front shape, crack thickness and crack plane profile are evaluated and their influence on the peak load, fracture displacement, and the critical stress intensity factor, $K_{IC}$ is studied. A new method of razor blade tapping was used, which utilized a guillotine-style razor tapping device to initiate the pre-crack and through-thickness compression to arrest it. A new approach of quantitatively characterizing the crack front shape using a two-parameter function is introduced. Surface features present on the pre-crack surface are classified and their effects on the post crack initiation behavior of the sample are analyzed. This study aims to identify and increase the understanding of the various factors that cause variation in the fracture toughness data of polymeric materials, thus leading to more informed engineering design decisions and evaluations. Chapters six and seven of Part II investigate the SHM capabilities of dispersed MWCNTs in mock, inert, and active energetics. In these experimental investigations, the strain and damage sensing abilities of multi-walled carbon nanotube (MWCNT) networks embedded in the binder phase of polymer bonded energetics (PBEs) are evaluated. PBEs are a special class of particulate composite materials that consist of energetic crystals bound by a polymer matrix, wherein the polymer matrix serves to diminish the sensitivity of the energetic phase to accidental mechanical stimuli. The structural health monitoring (SHM) approach presented in this work exploits the piezoresistive properties of the distributed MWCNT networks. Major challenges faced during such implementation include the low binder concentrations of PBEs, presence of conductive/non-conductive particulate phases, high degree of heterogeneity in the PBE microstructure, and achieving the optimal MWCNT dispersion. In chapter seven, Ammonium Perchlorate (AP) crystals as the oxidizer, Aluminum grains as the metallic fuel, and Polydimethylsiloxane (PDMS) as the binder are used as the constituents for fabricating PBEs. To study the effect of each constituent on the MWCNT network's SHM abilities, various materials systems are comprehensively studied: MWCNT/PDMS (nBinder) materials are first evaluated to study the binder's electromechanical response, followed by AP/MWCNT/PDMS (inert nPBE) to assess the impact of AP addition, and finally, AP/AL/MWCNT/PDMS (active nPBE-AL) to evaluate the impact of adding conductive aluminum grains. Compression samples (ASTM D695) were fabricated and subjected to monotonic compression. Electrical resistance is recorded in conjunction with the mechanical test via an LCR meter. Gauge factors relating the change in normalized resistance to applied strain are calculated to quantify the electromechanical response. MWCNT dispersions, and mechanical failure modes are analyzed via scanning electron microscopy (SEM) imaging of the fracture surfaces. Correlations between the electrical behavior in response to the mechanical behavior are presented, and possible mechanisms that influence the electromechanical behavior are discussed. The results presented herein demonstrate the successful ability of MWCNT networks as structural health monitoring sensors capable of real-time strain and damage assessment of polymer bonded energetics. / Doctor of Philosophy / The discovery of carbon nanotubes in 1990s popularized a new area of research in materials science called Nanoscience. Carbon nanotubes (CNTs) are one of several forms of Carbon, meaning a differently structured carbon molecule in the same physical state similar to diamonds, graphite, and coal. In the following decades, several carbon based nanoparticles were discovered or engineered and with the discovery of Graphene (GNP) in 2010, carbon based nanoparticles were propelled as the most promising class of nanoparticles. High mechanical strength and stiffness, excellent electrical and thermal conductivity, and high strength to weight ratios are some of the unique abilities of CNTs and GNPs which allow their use in a wide array of applications from aerospace materials to electronic devices. In the current work presented herein, CNTs and GNPs are added to polymeric materials to create a nanocomposite material, where the term "composite" refers to a material prepared with two or more constituent materials. The effects of this nanoparticle addition (a.k.a reinforcement) on the mechanical properties of the nanocomposite polymer materials are studied. Specifically, efforts are focused on studying fracture toughness, a material property that describes the material's ability to resist crack growth. Fracture toughness is a critical material property often associated with material and structural failures, and as such it is very important for safe and reliable engineering design of structures, components, and materials. Moving from a single function (i.e. mechanical enhancement) to a more multi-functional role, taking advantage of the excellent electrical and mechanical abilities of CNTs, a structural health monitoring system is developed for use in polymer bonded energetics (eg. solid rocket propellants). When a material undergoes mechanical deformation or damage, the measured electrical properties of the material undergo some change as well. Using sensor networks built with multiple CNTs dispersed within a polymeric material, a whole structure can be made into an effective sensor where by simply monitoring the electrical properties, the extent of material deformation and damage can be known. Such a system is geared towards providing early warning of impending catastrophic material failures thus directly improving the safety during material handling and operations.

<p>Polymer nanocomposites are a constantly evolving material category due to the ability to engineer the mechanical, thermal, and optical properties to enhance the efficiency of a variety of systems. While a vast amount of research has focused on the physical phenomena of nanoparticles and their contribution to the improvement of such properties, the ability to implement these materials into existing commercial or newly emerging processing methods has been studied much less extensively. The primary characteristic that determines which processing technique is the most viable is the rheology or viscosity of the material. In this work, we investigate the processing methods and properties of nanocomposites for thermal interface and radiative cooling applications. The first polymer nanocomposite examined here is a two-component PDMS with graphene filler for 3D printing via a direct ink writing approach. The composite acts as a thermal interface material which can enhance cooling between a microprocessor and a heat sink by increasing the thermal conductivity of the gap. Direct ink writing requires a shear thinning ink with specific viscoelastic properties that allow for the material to yield through a nozzle as well as retain its shape without a mold following deposition. No predictive models of viscosity for nanocomposites exist; therefore, several prominent models from literature are fit with experimental data to describe the change in viscosity with the addition of filler for several different PDMS ratios. The result is an understanding of the relationship between the PDMS component ratio and graphene filler concentration with respect to viscosity, with the goal of remaining within the acceptable limits for printing via direct ink writing. The second nanocomposite system whose processability is determined is paint consisting of acrylic filled with reflective nanoparticles for radiative cooling paint applications. The paint is tested with both inkjet and screen-printing procedures with the goal of producing a thermally invisible ink. Radiative cooling paint is successfully printed for the first time with solvent modification. This work evaluates the processability of polymer nanocomposites through rheological tailoring. </p><br>

In comparison with the high-pressure adsorption at room temperature, hydrogen adsorption at cryogenic temperatures can be significantly improved at low pressures, which has great potential for prospective mobile applications. In this study, a differential pressure based manometry system was designed and constructed for fast analysing hydrogen adsorption uptakes of sorbents up to a maximum of 10 wt% at 77 K and up to 11 bar. The safety design of the system in compliance with European ATEX directives (Zone 2) for explosive atmospheres was discussed in detail, together with additional pneumatic systems for remote control of the experiments. A thorough error analysis of related experimental tests was also performed. Common carbon sorbents, including several Norit branded activated carbons and graphene nanoplatelets (GNPs) with various surface areas, were characterised for their pore structures. The structural differences among GPNs of different surface areas were also studied. The hydrogen adsorption isotherms of these sorbents, examined in the newly-built manometry system, were further analysed and discussed with reference to the assessed microstructural properties. The carbonisation processes of plasma carbons from the microwave splitting of methane, and biochars from the pyrolysis of Miscanthus, were intensively studied primarily based on Raman spectroscopy, in conjunction with other characterisation techniques such as XRD, FTIR and XPS, for exploring the formation of graphitic structures and crystallinity under various conditions. Two selected types of carbons, the activated carbon AC Norit GSX with a specific surface areas of 875 m2/g and the graphene nanoplates with a specific surface area of 700 m2/g, were decorated with palladium nanoparticles in different compositions. The growth and distribution of doped palladium particles in the carbon substrates were studied, and their effects on porous properties and microstructures of the sorbents were also reviewed. Hydrogen adsorption tests of the decorated carbons were further conducted and discussed, to explore the potential effects of Pd contents on the adsorption kinetics and hydrogen absolute uptakes.